Metal Iodide Clusters And The Synthesis And Properties Of Coordination Polymers

The construction of supramolecular polymeric networks is of great interest in recent years, not only for their intriguing architectures and topologies, but also for their potential properties as functional solid materials in catalysis, optics and magnetism. In this paper, novel cluster and coordination polymers were designed by treatment of metal iodides with organic ligands. We found it is rarely studied at present. Therefore, it belongs to the leading field of crystal engineering.In this paper, eight novel cluster and coordination complexes were obtained by treating six nitrogen-containing ligands with metal iodides via the method of solvent diffuse under room temperature. Furthmore, we have investigated their syntheses, structural analyses, fluorescence properties and third-order nonlinear optical (NLO) properties.Firstly, the reactions of CuI, AgI, BiI₃ with L1 L3 ligands afford four new cluster coordination polymers: [(CuI)₄(bpp)₄]_n(1), [(AgI)₆(bpp)]_n(2), [Bi₂I₈(bpy)₂](bpyH)₂(3), [Bi₂I₈(Hbbbm)₂](4). 1 is the first uniform net of [2]-catenane nodes. Both of bridging iodides are also bound to another symmetry related Cu(I) thus forming a Cu(μ₂-I)₂Cu rhombohedron. The Cu(μ₂-I)₂Cu unit connects alternately two couples of bidentate bpp ligands, constituting an elliptic molecular ring. Each closed elliptic circuit is penetrated by the same loop from another chain at the loosest point. The two groups of interweaving chains display 2D "open" vertical interpenetration to give uniform (4,4) net, containing square intermolecular boxes. 2 represents the first example of 2-D bilayer AgI cluster motif. The structure of 2 is made up of uncoordinated organic ligand (bpp) and the infinite polymeric cluster [(AgI)₆]_n. The cluster can also be seen as a double layer (6,3) net motif composing of edge-sharing Ag₆I₆ hexagonal prism-shaped cell. 3 4 are two new organic-inorganic hybrids about bismuth(III) iodide. The third-order nonlinear optical (NLO) properties were detemined with a 7-ns pulsed laser at 532 nm. The result shows that polymer 1 gives large third-order NLO absorptive effects and strong refractive behaviors. Additionally, we find 1 has better fluorescent properties. The MO calculations were employed to polymer 1. The frontier molecular orbitals of 1 are all associated...